The present invention relates to specifically substituted metallocenes, a process for preparing them and their use in the polymerization of olefins.
Processes for preparing polyolefins with the aid of soluble, homogeneous catalyst systems comprising a transition metal component of the metallocene type and a cocatalyst component such as an aluminoxane, a Lewis acid or an ionic compound are known. These catalysts have a high activity and give polymers and copolymers having a narrow molar mass distribution.
In polymerization processes using soluble, homogeneous catalyst systems, thick deposits are formed on reactor walls and stirrer when the polymer is formed as a solid. These deposits are formed by agglomeration of the polymer particles whenever metallocene and/or cocatalyst are present in dissolved form in the suspension. Such deposits in the reactor systems have to be removed regularly, since they quickly attain considerable thicknesses, have a high strength and prevent heat exchange to the cooling medium. Such homogeneous catalyst systems cannot be used industrially in modern polymerization processes in the liquid monomer or in the gas phase.
To avoid deposit formation in the reactor, supported catalyst systems in which the metallocene and/or the aluminum compound serving as cocatalyst are/is fixed to an inorganic support material have been proposed.
EP-A-0,576,970 A1 discloses metallocenes and corresponding supported catalyst systems.
However, a frequent problem in the industrial use of supported catalyst systems is leaching of the metallocene component from the support material, resulting, for example, in undesirable deposit formation in the reactor.
It is an object of the present invention to find novel metallocenes which can be firmly fixed to a support and are not leached from the support material under industrially relevant polymerization conditions.
We have found that this object is achieved by specifically substituted metallocenes containing a cationic-group as substituent.
The present invention accordingly provides metallocenes of the formula (I), 
where
M1 is a transition metal of group 4 of the Periodic Table of the Elements, for example titanium, zirconium or hafnium, preferably zirconium,
R1 and R2 are identical or different and are each a hydrogen atom, a C1-C20 group, preferably a C1-C20-alkyl group, a C6-C14-aryl group, a C2-C20-alkenyl group, a C2-C20-alkynyl group, a C7-C20-alkylaryl group, each of which may bear one or more identical or different halogen atoms as substituents, a halogen atom, an xe2x80x94SiMe3 group or an OSiMe3 group; R1 and/or R2 are particularly preferably hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, branched pentyl, n-hexyl, branched hexyl, cyclohexyl or benzyl,
R3 are identical or different and are each a hydrogen atom or a C1-C40 group, preferably a C1-C20-alkyl group which may be substituted, in particular methyl, ethyl, trifluoroethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, hexyl, octyl, cyclopropyl, cyclopentyl or cyclohexyl, a C6-C14-aryl group which may be substituted, in particular phenyl, tolyl, xylyl, tert-butylphenyl, ethylphenyl, trifluoromethylphenyl, bis(trifluoromethyl)phenyl, methoxyphenyl, fluorophenyl, dimethylaminophenyl, trimethylammoniumphenyl iodide, dimethylsulfoniumphenyl bromide, triethylphosphoniumphenyl triflate, naphthyl, acenaphthyl, phenanthrenyl or anthracenyl, a C2-C20-alkenyl group, a C2-C20-alkynyl group, a C7-C20-alkylaryl group, a halogen atom, an SiMe3 group, an OSiMe3 group, a C1-C20-heterocyclic group which may be substituted, where the term heteroatom encompasses all elements with the exception of carbon and hydrogen, preferably atoms of groups 14, 15 or 16 of the Periodic Table of the Elements, and two radicals R3 may form a monocyclic or polycyclic ring system which may in turn be substituted, where at least one of the radicals R1, R2, R3 comprises a cationic group (xe2x80x94DEL)+Yxe2x88x92, where
D is an atom of group 15 or 16 of the Periodic Table of the Elements, preferably nitrogen, phosphorus, oxygen or sulfur,
E are identical or different and are each a hydrogen atom, a C1-C20 group, preferably a C1-C20-alkyl group, a C6-C14-aryl group, a C2-C20-alkenyl group, a C2-C20-alkynyl group or a C7-C20-alkylaryl group, a trialkylsilyl group, a triarylsilyl group, an alkylarylsilyl group which may be substituted, and two radicals E may form a monocyclic or polycyclic ring system which may in turn be substituted;
E is particularly preferably a hydrogen atom, methyl, ethyl, propyl, butyl, allyl, benzyl, methoxymethyl, benzyloxymethyl, 2-methoxyethoxymethyl, 2-trimethylsilylethoxymethyl, trimethylsilyl;
L is 3 when D is an atom of group 15 of the Periodic Table of the Elements and is 2 when D is an atom of group 16 of the Periodic Table of the Elements,
Y is halide, C1-C10-alkylsulfonate, C1-C10-haloalkylsulfonate, C6-C20-arylsulfonate, C6-C20-haloarylsulfonate, C7-C20-alkylarylsulfonate, C1-C20-haloalkylcarboxylate, C1-C10-alkyl sulfate, tetrafluoroborate, hexafluorophosphate, hexafluoroantimonate, hexafluoroarsenate; Y is preferably chloride, bromide, iodide, triflate, mesylate, tosylate, benzenesulfonate, trifluoroacetate, methyl sulfate, tetrafluoroborate or hexafluorophosphate;
m is an integer less than or equal to 4 and greater than or equal to 1, preferably 1 or 2, particularly preferably 1,
mxe2x80x2 is an integer less than or equal to 4 and greater than or equal to 1, preferably 1 or 2, particularly preferably 1,
k is zero or 1, where the metallocene is unbridged when k=0 and is bridged when k=1,
A is a bridge of the following type 
xe2x80x83or xe2x95x90BR4, AIR4, xe2x80x94Sxe2x80x94, xe2x80x94SOxe2x80x94, xe2x80x94SO2xe2x80x94, xe2x95x90NR4, xe2x95x90PR4, xe2x95x90P(O)R4, o-phenylene, 2,2xe2x80x2-biphenylene, where
M2 is carbon, silicon, germanium, tin, nitrogen or phosphorus, preferably carbon, silicon or germanium, in particular carbon or silicon,
o is 1, 2, 3 or 4, preferably 1 or 2,
R4 and R5 are identical or different and are each a hydrogen atom, halogen, a C1-C20 group, preferably C1-C20-alkyl, in particular a methyl group, C6-C14-aryl, in particular a phenyl or naphthyl group, C1-C10-alkoxy, C2-C10-alkenyl, C7-C20-arylalkyl, C7-C20-alkylaryl, C6-C10-aryloxy, C1-C10-fluoroalkyl, C6-C10-haloaryl, C2-C10-alkynyl, C3-C20-alkylsilyl, in particular trimethylsilyl, triethylsilyl, tert-butyldimethylsilyl, C3-C20-arylsilyl, in particular triphenylsilyl, or C3-C20-alkylarylsilyl, in particular dimethylphenylsilyl, diphenylsilyl or diphenyl-tert-butylsilyl, and R4 and R5 may form a monocyclic or polycyclic ring system;
A is preferably dimethylsilanediyl, dimethylgermanediyl, ethylidene, methylethylidene, 1,1-dimethylethylidene, 1,2-dimethylethylidene, tetramethylethylidene, isopropylidene, phenylmethylmethylidene, diphenylmethylidene, particularly preferably dimethylsilanediyl or ethylidene;
The radicals X are identical or different and are each a hydrogen atom, a halogen atom such as fluorine, chlorine, bromine or iodine, a hydroxyl group, a C1-C10-alkyl group such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, hexyl, cyclohexyl, a C6-C15-aryl group such as phenyl, naphthyl, a C1-C10-alkoxy group such as methoxy, ethoxy, tert-butoxy, a C6-C15-aryloxy group, a benzyl group, preferably a chlorine atom, a fluorine atom, a methyl group, a benzyl group, particularly preferably a chlorine atom or a methyl group.
Particularly preferred novel metallocenes of the formula (I) have the formula (I*), 
where
M1, A, R1, k and X are as defined in formula (I) and
R6 are identical or different and are each a hydrogen atom or a C1-C40 group, preferably a C1-C20-alkyl group which may be substituted, in particular methyl, ethyl, trifluoromethyl, trifluoroethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, hexyl, octyl, cyclopropyl, cyclopentyl, cyclohexyl, a C6-C14-aryl group which may be substituted, e.g. phenyl, a C2-C20-alkynyl group, a C7-C20-alkylaryl group, halogen, an OR4 group, an SiR43 group, an NR42 group, an SR4 group, and two radicals R4 and R6 may each or together form a monocyclic or polycyclic ring system which may in turn be substituted, where R4 is as defined in formula (I) and at least one of the radicals R6 bears or is a cationic group (xe2x80x94DEL)+Yxe2x88x92, where D, E, L and Y are as defined in formula (I),
q is an integer less than or equal to 5 and greater than or equal to 1, preferably 1 or 2, particularly preferably 1, and
qxe2x80x2 is an integer less than or equal to 5 and greater than or equal to 1, preferably 1 or 2, particularly preferably 1.
Illustrative but nonrestrictive examples of novel metallocenes of the formula (I) are:
dimethylsilanediylbis(2-methyl-4-(4xe2x80x2-trimethylammoniumphenyl)indenyl)dichlorozirconium diiodide
dimethylsilanediylbis(2-methyl-4-(4xe2x80x2-trimethylammoniumphenyl)indenyl)dichlorotitanium diiodide
dimethylsilanediylbis(2-methyl-4-(4xe2x80x2-trimethylammoniumphenyl)indenyl)dichlorohafnium diiodide
dimethylsilanediylbis(2-methyl-4-(3xe2x80x2-trimethylammoniumphenyl)indenyl)dichlorozirconium diiodide
dimethylsilanediylbis(2-methyl-4-(2xe2x80x2-trimethylammoniumphenyl)indenyl)dichlorozirconium diiodide
dimethylsilanediylbis(2-methyl-4-(3xe2x80x2,5xe2x80x2-bis(trimethylammonium)phenyl)indenyl)-dichlorozirconium tetraiodide
dimethylsilanediylbis(2-methyl-4-(4xe2x80x2-trimethylammoniumnaphthyl)indenyl)dichlorozirconium diiodide
dimethylsilanediylbis(2-methyl-4-(4xe2x80x2-trimethylammoniumphenyl)indenyl)dichlorozirconium ditosylate
dimethylsilanediylbis(2-ethyl-4-(4xe2x80x2-trimethylammoniumphenyl)indenyl)dichlorozirconium ditriflate
dimethylsilanediylbis(2-methyl-4-(4xe2x80x2-dimethylammoniumphenyl)indenyl)dichlorozirconium dichloride
dimethylsilanediylbis(2-methyl-4-(4xe2x80x2-trimethylammoniumphenyl)indenyl)dichlorozirconium bistetrafluoroborate
dimethylsilanediylbis(2-methyl-4-(4xe2x80x2-N-methyl-N-pyrrolidinophenyl)indenyl)-dichlorozirconium diiodide
dimethylsilanediylbis(2-methyl-4-(4xe2x80x2-dimethylammoniumphenyl)indenyl)dichlorotitanium dichloride
dimethylsilanediylbis(2-methyl-4-(4xe2x80x2-dimethyl(methoxymethyl)ammoniumphenyl)-indenyl)dichlorozirconium dichloride
dimethylsilanediylbis(2-methyl-4-(4xe2x80x2-dimethyl (2xe2x80x3-methoxyethoxymethyl)-ammoniumphenyl)indenyl)dichlorozirconium dichloride
dimethylsilanediylbis(2-methyl-4-(4xe2x80x2-dimethyl(benzyloxymethyl)ammoniumphenyl)-indenyl)dichlorozirconium dichloride
dimethylsilanediylbis(2-methyl-4-(4xe2x80x2-dimethyl(2xe2x80x3-trimethylsilylethoxymethyl)-ammoniumphenyl)indenyl)dichlorohafnium dichloride
dimethylsilanediylbis(2-methyl-4-(4xe2x80x2-dimethylbenzylammoniumphenyl)indenyl)-dichlorozirconium dichloride
dimethylsilanediylbis(2-methyl-4-(4xe2x80x2-dimethylallylammoniumphenyl)indenyl)dichlorozirconium diiodide
dimethylsilanediylbis(2-methyl-4-(4xe2x80x2-triethylammoniumphenyl)indenyl)dichlorozirconium diiodide
dimethylsilanediylbis(2-ethyl-4-(4xe2x80x2-dimethyl (2xe2x80x3-trimethylsilylethoxymethyl)ammoniumphenyl)indenyl)dichlorohafnium dichloride
dimethylsilanediylbis(2-ethyl-4-(4xe2x80x2-dimethylbenzylammoniumphenyl)indenyl)dichlorozirconium dichloride
dimethylsilanediylbis(2-ethyl-4-(4xe2x80x2-dimethylallylammoniumphenyl)indenyl)dichlorozirconium diiodide
dimethylsilanediylbis(2-ethyl-4-(4xe2x80x2-trimethylammoniumphenyl)indenyl)dichlorozirconium diiodide
dimethylsilanediylbis(2-n-butyl-4-(4xe2x80x2-trimethylammoniumphenyl)indenyl)dichlorozirconium diiodide
dimethylsilanediylbis(2-isopropyl-4-(4xe2x80x2-triethylammoniumphenyl)indenyl)dichlorozirconium dibromide
dimethylsilanediylbis(2-isobutyl-4-(4xe2x80x2-triethylammoniumphenyl)indenyl)dichlorozirconium ditriflate
dimethylsilanediylbis(2-ethyl-4-(4xe2x80x2-triethylphosphoniumphenyl)indenyl)dichlorozirconium diiodide
dimethylsilanediylbis(2-methyl-4-(4xe2x80x2-dimethylsulfoniumphenyl)indenyl)dichlorozirconium dibromide
dimethylsilanediylbis(2-ethyl-4-(4xe2x80x2-dimethylsulfoniumphenyl)indenyl)dichlorozirconium dibromide
dimethylsilanediylbis(2-methyl-4-(3xe2x80x2-dimethylsulfoniumphenyl)indenyl)dichlorozirconium dibromide
dimethylsilanediylbis(2-methyl-4-(2xe2x80x2-dimethylsulfoniumphenyl)indenyl)dichlorozirconium dibromide
dimethylsilanediylbis(2-methyl-4-(3xe2x80x2,5xe2x80x2-bis(dimethylsulfonium)phenyl)indenyl)dichlorozirconium tetrabromide
dimethylsilanediylbis(2-methyl-4-(4xe2x80x2-dibenzylsulfoniumphenyl)indenyl)dichlorozirconium dibromide
dimethylsilanediylbis(2-methyl-4-(4xe2x80x2-methyl(methoxymethyl)sulfoniumphenyl)indenyl)dichlorozirconium dichloride
dimethylsilanediylbis(2-methyl-4-(4xe2x80x2-diallylsulfoniumphenyl)indenyl)dichlorozirconium dibromide
dimethylsilanediylbis(2-methyl-4-(3xe2x80x2-diphenylethylphosphoniumphenyl)indenyl)dichlorozirconium diiodide
dimethylsilanediylbis(2-methyl-4-(3xe2x80x2-trimethylphosphoniumphenyl)indenyl)dichlorozirconium ditriflate
methylphenylsilanediylbis(2-isobutyl-4-(4xe2x80x2-triethylammoniumphenyl)indenyl)-dichlorozirconium ditosylate
1,2-ethanediylbis(2-methyl-4-(3xe2x80x2-dimethylammoniumphenyl)indenyl)dichlorozirconium bistrifluoroacetate
1,2-ethanediylbis(2-methyl-4-(4xe2x80x2-dimethylsulfoniumphenyl)indenyl)dichlorozirconium dibromide
1,2-ethanediylbis(2-methyl-4-(3xe2x80x2-diphenylethylphosphoniumphenyl)indenyl)dichlorozirconium diiodide
dimethylsilanediylbis(2-methyl-5-trimethylammoniumindenyl)dichlorozirconium dichloride
dimethylsilanediylbis(2-methyl-5-trimethylphosphoniumindenyl)dichlorozirconium dichloride
1,2-ethanediylbis(2-methyl-4-dimethylbenzylammoniumindenyl)dichlorozirconium dibromide
1,2-ethanediylbis(2-methyl-4-phenyl-5-dimethylbenzylammoniumindenyl)dichlorozirconium dibromide
dimethylsilanediylbis(2-methyl-4-phenyl-6-trimethylammoniumindenyl)dichlorozirconium dichloride
dimethylsilanediylbis(2-methyl-5-dimethylsulfoniumindenyl)dichlorozirconium dibromide
dimethylsilanediylbis(2-methyl-4-(4xe2x80x2-(2xe2x80x3-trimethylammoniumethyl)phenylindenyl)dichlorozirconium dichloride
dimethylsilanediylbis(2-methyl-4-(4xe2x80x2-(3xe2x80x3-dimethylsulfoniumpropyl)phenylindenyl)dichiorozirconium diiodide
dimethylsilanediylbis(2-methyl-4-(3xe2x80x2-(2xe2x80x3-trimethylammoniumethyl)phenylindenyl)dichlorozirconium dichloride
dimethylsilanediylbis(2-methyl-4-(2xe2x80x3-trimethylammoniumethyl)indenyl)dichlorozirconium dichloride
dimethylsilanediylbis(2-(2xe2x80x2-trimethylammoniumethyl)indenyl)dichlorozirconiumdichloride
dimethylsilanediylbis(2-(2xe2x80x2-trimethylammbniumethyl)-4-phenylindenyl)dichlorozirconium dibromide
dimethylsilanediylbis(2-(2xe2x80x2-dimethylsulfoniumethyl)-4,6-dimethylindenyl)dichlorozirconium diiodide.
The present invention further provides a process for preparing metallocenes of the formula (I). The process of the present invention comprises reacting a metallocene of the formula (Ia) with a reagent EY to give a metallocene of the formula (I). 
The radicals R1, R2, R3, A, M1, X, E, Y, k, m and mxe2x80x2 are as defined in formula (I), and R7 are identical or different and are each a hydrogen atom or a C1-C40 group, preferably a C1-C20-alkyl group which may be substituted, in particular methyl, ethyl, trifluoroethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, hexyl, octyl, cyclopropyl, cyclopentyl, cyclohexyl, a C6-C14-aryl group which may be substituted, in particular phenyl, tolyl, xylyl, tert-butylphenyl, ethylphenyl, trifluoromethylphenyl, bis(trifluoromethyl)phenyl, methoxyphenyl, fluorophenyl, dimethylaminophenyl, methylthiophenyl, diethylphosphinophenyl, naphthyl, acenaphthyl, phenanthrenyl, anthracenyl, a C2-C20-alkenyl group, a C2-C20-alkynyl group, a C7-C20-alkylaryl group, a halogen atom, an SiMe3 group, an OSiMe3 group, a C1-C20-heterocyclic group which may be substituted, where the term heteroatom encompasses all elements with the exception of carbon and hydrogen and preferably refers to atoms of groups 14, 15 and 16 of the Periodic Table of the Elements, and two radicals R7 may form a monocyclic or polycyclic ring system which may in turn be substituted.
The metallocene of the formula (Ia) bears a group DEL1 on at least one of the radicals R1, R2, R7, where D is an atom of group 15 or 16 of the Periodic Table of the Elements, in particular nitrogen, phosphorus, oxygen or sulfur, and E and L are as defined in formula (I).
The preparation of metallocenes of the formula (Ia) is carried out by methods known from the literature (e.g. EP-A-0,576,970; Chem. Lett., 1991, 11, p.2047 ff; Journal of Organometallic Chem., 288 (1985) 63-67 and documents cited therein).
The reagent EY is a compound capable of transferring the radical E, where E and Y are as defined in formula (I).
Illustrative but nonrestrictive examples of the reagent EY are:
methyl iodide, methyl bromide, methyl chloride, methyl triflate, methyl trifluoroacetate, methyl methanesulfonate, methyl p-toluenesulfonate, dimethyl sulfate, trimethyloxonium tetrafluoroborate, trimethyloxonium hexafluorophosphate, ethyl iodide, ethyl bromide, ethyl chloride, triethyloxonium tetrafluoroborate, triethyloxonium hexafluorophosphate, propyl iodide, propyl bromide, propyl triflate, butyl bromide, butyl iodide, butyl chloride, pentyl bromide, octyl bromide, benzyl chloride, benzyl bromide, benzyl triflate, allyl bromide, allyl chloride, p-methoxybenzyl chloride, trimethylsilyl chloride, trimethylsilyl bromide, trimethylsilyl iodide, timethylsilyl triflate, tert-butyldimethylsilyl chloride, tert-butyldimethylsilyl triflate; triphenylsilyl chloride, triphenylsilyl iodide, triphenylsilyl triflate, methoxymethyl chloride (MOMCl), 2-methoxyethoxymethyl chloride (MEMCl), 2-trimethylsilylethoxymethyl chloride (SEMCl), benzyloxymethyl chloride (BOMCl), hydrogen fluoride, hydrogen chloride, hydrogen bromide, hydrogen iodide, trifluoroacetic acid, methanesulfonic acid, trifluoromethanesulfonic acid, p-toluenesulfonic acid, sulfuric acid, perchloric acid, acetic acid, triethylamine hydrochloride, trimethylamine hydrofluoride, tetrafluoroboric acid diethyl etherate, hexafluorophosphoric acid.
The process of the present invention can be carried out in the presence of a suitable solvent or in bulk. Nonrestrictive examples of suitable solvents are hydrocarbons which may be halogenated, for example benzene, toluene, xylene, mesitylene, ethylbenzene, chlorobenzene, dichlorobenzene, fluorobenzene, decalin, pentane, hexane, cyclohexane, dichloromethane, chloroform, tetrachloromethane, 1,2-dichloroethane, trichloroethylene, ethers such as diethyl ether, di-n-butyl ether, MTBE, THF, DME, anisole, triglyme, dioxane, amides such as DMF, dimethylacetamide, NMP, sulfoxides such as DMSO, phosphoramides such as hexamethylphosphoramide, urea derivatives such as DMPU, ketones such as acetone, ethyl methyl ketone, esters such as ethyl acetate, nitrites such as acetonitrile and also any mixtures of these substances.
The process of the present invention is generally carried out in a temperature range from xe2x88x92100xc2x0 C. to +500xc2x0 C., preferably in a temperature range from xe2x88x9278xc2x0 C. to +200xc2x0 C., particularly preferably at from 0xc2x0 C. to 100xc2x0 C.
The reaction can be carried out in a single-phase system or in a multiphase system.
The molar ratio of reagent EY to metallocene (Ia) is generally in the range from 0.5 to 100, preferably from 1 to 10.
The concentration of metallocene (Ia) or of reagent EY in the reaction mixture is generally in the range from 0.001 mol/l to 8 ml/l, preferably in the range from 0.01 to 3 mol/l, particularly preferably in the range from 0.1 mol/l to 2 mol/l.
The reaction time for the reaction of metallocenes of the formula (Ia) with a reagent EY is generally in the range from 5 minutes to 1 week, preferably in the range from 15 minutes to 48 hours.
The compounds of the present invention are particularly suitable as constituents of catalyst systems for the polymerization of olefins based on ethylene, propylene, norbornadiene and also of functionalized olefins, with both homopolymers and copolymers being obtainable.